Combatting arthropods with phenylhydrazones of 1,2-dicarbonyl compounds

ABSTRACT

A-(HALO, CYANO, NITRO AND AZIDO)-A-(ALKANOYL, CARBOALKOXY (I.E. ALKOXY CARBONYL), AMINO AND MONO- AND DIALKYLAMINO)-CARBONYL-(UNSUBSTITUTED AND MOMO TO PENTA ALKYL AND/OR ELECTRONEGATIVE SUBSTITUENT (E.G. HALO, NITRO, CYANO, TRIFLUOROMETHYL, TRIFLUOROMETHYL-MERCAPTO, SULFONYL, AND -SULFOXYL, ALKOXY, ALKYL SULFONYL AND/OR DIMETHYLAMINO SULFONYL)-SUBSTITUTED) PHENYL HYDRAZONES AND THEIR CORRESPONDING ALKALI METAL, ALKALINE EARTH METAL AND AMINE SALTS, WHICH POSSES PERTICIDAL, ESPECIALLY ACARICIDAL AND INSECTICIDAL, PROPERTIES AND WHICH MAY BE PRODUCED BY CONVENTIONAL METHODS.

United States Patent US. Cl. 424--304 Claims ABSTRACT OF THE DISCLOSURE u-(Halo, cyano, nitro and azido)a-(alkanoyl, carboalkoxy [i.e. alkoxy carbonyl], amino and monoand dialkyl amino)-carbonyl-(unsubstituted and mono to penta alkyl and/or electronegative substituent [e.g. halo, nitro, cyano, trifiuoromethyl, trifluoromethyl-mercapto, -sulfonyl, and -sulfoxyl, alkoxy, alkyl sulfonyl and/or dimethylamino sulfonyl1-substituted) phenyl hydrazones and their corresponding alkali metal, alkaline earth metal and amine salts, which possess pesticidal, especially --acaricidal and insecticidal, properties and which may be produced by conventional methods.

This application is a division of US. patent application Ser. No. 762,155, filed Sept. 24, 1968, now US. Pat. No. 3,641,098.

The present invention relates to and has for its objects the provision for new phenylhydrazones of 1,2-dicarbonyl compounds, i.e. a s-substituted carbonyl-phenylhydrazones or N-(carbonyl-methyleneimino)-anilines, which possess pesticidal, especially insecticidal and acaricidal, properties, active compositions in the form of mixtures of suchwompounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. arthropids, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is already known that certain phenylhydrazones of dicyanoketone, for example a,a-dicYaI10-CaI'bOI1Y1-2,5dlchlorophenylhydrazone (A) can be used for the control of insects and mites (see US. Pat. 3,157,569).

It has been found in accordance with the present invention that the new phenylhydrazones of the formula Z is C alkyl, alkoxy, or an electronegative substituent, m is a whole number from 1 to 5,

and their alkali metal salts, alkaline earth metal salts and amine salts, exhibit strong pesticidal, especially insecti- Cidal and acaricidal, properties.

"ice

The present invention further provides a process for the production of the new compounds of Formula I above in which [a] A diazotized amine of the formula Z and m are the same as defined above, and A stands for an anion introduced by the diazotization,

is reacted, optionally in the presence of a solvent, with an active methylene compound of the formula (Ila) in which (Ilb) in which X and Y are the same as defined above, or

[b] A diazotization product of an amine according to Formula Ila above is reacted with a 2-halogen-l,3-dicarbonyl compound of the formula CHzCO Hal 0 H \CY H (He) in which Y is the same as defined above, and Hal is halogen such as chloro, bromo, iodo or fluoro,

optionally in the presence of a solvent, or

[c] A phenylhydrazone compound of the formula Hal in which Y, Z and m are the same as defined above, and

Hal is halogen such as chloro, bromo, iodo or fluoro,

is reacted, optionally in the presence of a solvent, with an alkali metal salt of the formula MeX' 9n in which Me is an alkali metal such as sodium, potassium or lithium, and X is cyano, azido or nitro.

and acaricidal effectiveness than the chemically very similar previously know phenylhydazones.

If 3,5-bis(trifluoromethyl)aniline, which was diazotized in phosphoric acid with nitrosyl-sulfuric acid at -l0 C., and cyano-acetic acid methyl ester are used as starting materials, the reaction course of the process variant [a] can be represented by the following equation:

/CN N=N A; Cl?

CO CH: Fa 2 1 (IIba) If 2-chloroS-trifiuoromethyl-aniline, which was diazotizcd in concentrated hydrochloric acid with NaNO and a-chloro-acetyl-acetone are used as starting materials, a phenylhydrazone according to the present invention is obtained which can be reacted for example with KCN, to give a further phenylhydrazone according to the present invention.

The reaction course according to process variants [b] and [c] is represented by the following overall equation:

The starting materials (Ila), (Ilb) and (He) used for process variants [a] and [b], as well as the starting materials (lId) used for process variant [0] are already known and can be prepared in simple manner according to known processes. The starting materials (I) used for process variant [0] are new compounds of the present invention and, of course, are obtained according to the process variants [a] and [b].

Advantageously, in accordance with the present invention, in the various formulae herein:

X represents halo such as chloro, bromo, iodo and fluoro, especially chloro and bromo, and particularly chloro; cyano; nitro; or azido, i.e. N;,; Y represents straight and branched chain alkyl having 1-4 carbon atoms such as methyl to tert.-butyl inclusive, especially methyl, ethyl, nand iso-propyl, n-, isoand sbutyl, and the like, more particularly alkyl having l-3 carbon atoms, and preferably methyl; straight and branched chain alkoxy having 14 carbon atoms such as methoxy to tert.-butoxy inclu- 4 sive, especially methoxy, ethoxy, nand isoand s-butoxy, and the like, more particularly alkoxy having l-3 carbon atoms, and preferably methoxy and ethoxy; or -NRR' in which R and R each individually represents hydrogen or alkyl having l-3 carbon atoms such as methyl to isopropyl inclusive as defined above; especially amino (NH and monoand di-methyl amino; Z represents straight and branched chain alkyl or alkoxy having 1-4 carbon atoms such as methyl to tert.-butyl inclusive as defined above for Y, more particularly alkyl having l-3 carbon atoms, and preferably methyl and ethyl, and mixtures thereof; and/or electronegative substituents such as halo, such as chloro, bromo, iodo and/or fiuoro, especially chloro, fluoro and/or bromo, and more particularly chloro and/or fluoro; nitro; cyano; difiuoromethyl; trifiuoromethyl; trifiuoromethylmercapto, i.e. CF S; difiuorochloromethylmercapto, i.e. CF Cl-S; trifiuoromethyl sulfonyl, i.e. CF SO trifluoromethyl sulfoxyl, i.e. CF SO-; alkyl sulfonyl having 1-4 carbon atoms such as methyl to tert.-butyl inclusive, as defined above, -sulfonyl, especially C alkyl sulfonyl, and more especially methyland ethylsulfonyl, i.e. C alkyl-SO dimethylamino sulfonyl, i.e. (CH NSO and m is a whole number from 1 to 5, especially 1 to 4 or The corresponding salts of the instant compounds include the alkali metal salts such as the Na, K, Li, etc. salts, the alkaline earth metal salts such as the Ca, Mg, Ba, Sr, etc. salts, and the amine salts such as secondary and tertiary amine salts such as tri C alkyl and C alkyl-phenyl amines, e.g. tri, same and mixed methyl to butyl-amine, methyl to butyl-phenylamine, etc., especially triethyl and ethyl-phenyl amines.

Preferably, X is chloro, bromo, cyano, nitro or azido, Y is C alkyl, C alkoxy, amino or monomethylamino, Z is C alkyl, chloro, fiuoro, nitro, cyano, difluoromethyl, difluorochloromethylmercapto, trifluoromethylmercapto, trifluoromethylsulfonyl, C alkylsulfonyl, dimethylaminosulfonyl, and/or methoxy, with in being 1-5.

In particular, X is chloro or cyano; Y is C alkyl or C alkoxy, Z is methyl, chloro, nitro, trifluoromethyl, trifiuoromethylmercapto and/or trifiuoromethylsulfonyl, with m being 1-5, preferably 14 or 1-3.

It will be realized that the process variants [a] and [b] are carried out under practically the same reaction conditions.

As solvents, water and Water-miscible organic solvents are suitable. These include alcohols such as methanol and ethanol, as well as acetic acid, and the like. The organic solvents serve as solubilizcr for the methylene component. The reaction is preferably carried out in a pH range of about 4-8. For the bulfering of the mineral acids present in the reaction mixture, bases such as sodium acetate, sodium carbonate, sodium hydroxide, and the like, are added.

The reaction temperatures used are, in general, substantially between about 20 to +30 C., preferably from about l0 to +20 C.

When carrying out the reaction, the starting materials are preferably used in equimolar proportions, the methylene or dicarbonyl component optionally in a small excess. The reaction is, in general, complete after 26 hours, it being preferable in many cases to continue stirring for several hours at room temperature. The phenylhydrazones of the present invention are, in general, obtained in crystalline form and can be isolated by filtration from the reaction mixture. 7

When carrying out process variant [0], the work is accomplished in similar manner. The same solvents and solvent mixtures are used. In this case, however, the pH value is not important. The temperatures used are, in general, substantially between about'0 to 80 C., preferably from about 20 to 70 C.

The phenylhydrazones of the present invention obtained according to the three variants of the process can be converted in the usual manner into their alkali metal salts, alkaline earth metal salts and amine salts. Particularly useful are the sodium, potassium, calcium, magnesium, triethylamine and ethyleniline salts.

The preparation of these solutions is carried out in the usual manner, for example by dissolving the instant phenylhydrazones in organic solvents such as alcohols and adding the appropriate bases. The salts are in most cases sparingly soluble and precipitate, but can also be precipitated with ether. It is also possible to evaporate the solvent.

Advantageously, the active compounds according to the present invention exhibit strong insecticidal and acaricidal activities, with low phytotoxicity and relatively low mammalian toxicity. The active compounds can, therefore, be used with good results for the control of noxious sucking and biting insects, Diptera as well as mites (Acarina). The effects set in rapidly and are long-lasting.

To the sucking insects contemplated herein, there belong aphids, such as the green peach aphid (Myzus ample in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), parafiins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylp ersicae), the bean aphid (Doralis fabae); scales, suchas Aspidiotus hederae, Lecanz'um hesperidum, Pseudococcus maritimus; Thysanoptera, such as H ercinothrips femoralis; and bugs, such as the beet bug (Piesma quadrata) and the bed bug (Cimex lectularius), and the like.

With the biting insects contemplated herein, there are classed butterfly caterpillars, such as Plutella maculipenm's, Lymantria dispar; beetles, such as granary weevils (Sitophilus granarius), the Colorado bettle (Leptinotarsa decemlineata), but also species living in the soil, such as the wireworms (Agriotes sp.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such. as the German cockroach (Blattellzi g'ehnanica); Orthoptera, such as the house cricket (Gryllus domesticus); termites, such as Reticulitermes; Hymenoptera, such as ants, and the like.

The Diptera contemplated herein comprise in particular.

the flies, such as the vinegar fly (Drosophila m'elanogaster), the Mediterranean fruitfly (Ceratz'tis capitata), the house fly (M usca domestica) and mosquitoes, such as the yellow fever mosquito (Aedes aegypti), and the like.

In the case of the mites contemplated herein, particularly important are the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetranychus telarius" or urticae), the European red mite (Paratetranychus piloszis); blister mites, such as the currant blister mite (Eriophyes ribis) and tarsonemids, such as Tarsonemus pallidus, andticks, and the like.

If the instant phenylhydrazones are used in the formof their corresponding salts, their effectiveness changes, in general, only extremely slightly;

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional pesticidal diluents or extenders, i.e. conventional dispersible carrier vehicles, such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticidal 'dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticidal surface-active agents, including emulsifying agents and/or dispersing agents, whereby for exene chloride, etc.), alcohols (e.g.. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.), and/or Water; as Well as dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl aryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.-

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides, insecticides, fungicides, herbicides, bactericides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and preferably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.001-% or even 20-80%, but

preferably 0.00l-5%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional pesticidal dispersible carrier vehicle such as (1) a dispersible carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water, preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is efiective for the purpose in question and which is generally between about 0.001- and preferably 0.00l-'80%, by weight of themixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment in extremely finely divided form, i.e. mist form, for example by airplane crop spraying techniques. Only a few liters/hectare are needed, and often amounts up to about 1 quart/ acre, preferably 216 fluid ounces/ acre, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 40 to about 95% by Weight of active compound or even the active substance alone, e.g. about 40- 100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively controlling or combating pests, e.g. arthropods, i.e. insects and acarids, and more particularly, methods of combating at least one of insects and acarids which comprises applying to at least one of correspond- 8 EXAMPLE 1 Plutella test Solvent 3 parts by weight dimethyl formamide.

, Emulsifier: 1 art b wei ht alk lar l 01 1 col ether. ingly (a) such insects, (b) such acarrds, and (c) the cor- 5 p y g y y P yg y responding habitat, i.e. the locus to be protected, a cor- To produce a suitable preparation of the particular respondingly combative amount, i.e. an arthropodicidally, active compound, 1 part by weight of such active comespecially insecticidally or acaricidally, effective amount pound is mixed with'the stated amount of solvent containof the particular active compound of the invention alone 10 ing the stated amount of emulsifier and the resulting conor together with a carrier vehicle as noted above. The centrate is diluted with water to the desired final conceninstant formulations or compositions are applied in the tration. usual manner, for instance by spraying, atomizing, vapor- Cabbage leaves (Brassica oleracea) are sprayed with izing, scattering, dusting, watering, sprinkling, pouring, the preparation of the given active compound until dew and the like. 15 moist and are then infested with caterpillars of the It will be realized, of course, that the concentration of diamond back moth (Plutella maculipennis). the particular active compound utilized in admixture with After the specified period of time, the degree of destructhe carrier vehicle will depend upon the intended applition is determined as a percentage: 100% means'that all catiOm'Iherefore, in special cases it is possible to go above the caterpillars are killed whereas 0% means that none or below the aforementioned concentration ranges. of the caterpillars are-killed.

The outstanding activity of the new compounds of the The particular activecompounds tested, their concenpresent invention is illustrated without limitation by the trations, the evaluation time and the results obtained can following examples. be seen from the following Table 1: I

TABLE (Plant-damaging insects] Concentretion 4 Degree of of active destruction compound in in percent Active compound percent attera days (A) Cl '7 ON at a N-N=C\ 21 CN 1 (known) (41 Cl 0.2 100 ON 0.02 I 100 c1 I;IN=O

' l H I .o-ocnr.

51) Cl 0.2 100 ON 0.02 100 otN N-N=C 1 1 I C-O C:H|

-. o-oon,

COC;H|

( -0on1 o TABLE 1-Continued Concentratlon Degree of of active destruction compound in in percent Actlve compound percent after 8 days (91) G1 0.2 100 0.02 100 N--N=C 0.002 50 C-CH: l l

(101) CI 0.2 100 0.02 100 C1 N-N=C\ 1k C-CH:

(111) 01 0.2 100 0.02 100 1 NN=C\ (:1 1k C-OCnH EXAMPLE 2 25 A further test was carried out in the same manner as Example 1 and the results are set out below in Table 2.

TABLE 2 [Plant-damaging lnseets] Concentratlon Degree of of active destruction compoundin in percent Active compound percent alter 3 days (12;) Cl 0. 2 100 CN 0.02 100 0.002 60 N-N=C C-CH: 1 I

(131) Cl 0. 2 100 /CN 0.02 100 N-N=C\ & (CHa)n (14;) CN 0.2 100 l 0.02 100 C1 NN=C\ (1: 1 C-CH:

(151) .4 G1 0.2 100 ON 0. 02 100 Cl NN=O k CC(CH:)|

(16 ON 0.2 100 0.02 100 C1 N-N=C I C-C(CHI)I F: ll

(17 FzC 0.2 100 C N L0. 02 100 N-N=C Ha): F: H

(18 CN 0.2 100 0. 02 100 FsC-S -]1 !l-N=C\ 0.002 90 C-CH:

11 EXAMPLE 3 Phaedon larvae test Solvent: 3 parts by weight dimethyl formamide.

Emulsifier: 1 part by weight alkylaryl polyglycol ether. 5

To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed with the stated amount of solvent con taining the stated amount of emulsifier, and the resulting concentrate is diluted with water to the desired final 10 concentration.

TABLE 3 [Plant-damaging insects] Concentration Degree 01 of active destruction compound in in percent Active compound percent after 3 days (A) Cl 0. 2 100 /CN 0. 02 NN=C (known) (191)... C1 0. 2 100 UN 0. 02 100 NN=C (43).-.-::: CI 0.2 100 CN 0. 02 100 N-N=C\ C--O 02H: 1 l

(201) 0N 0.2 100 0.02 100 NN=O\ 0. 002 50 0-0 CH: F:

(21;).. CN 0.2 100 0.02 100 N--N=C C-O (11 l I (221) ....'::a Cl 0. 2 100 /CN 0. 02 100 N-N=C\ C-O (32 1 I (23 CHI 0.2 100 C1 0. 02 100 t NN=C C-CHI HI ll 1 3 EXAMPLE 4 A further test was carried out in the same manner as Example 3 and the results are set out below in Table 4:

Bean plants (Phaseolus vulgaris), which have a height These bean plants are then heavily infested with'spider' of approximately 10-30 cm., are sprayed with the preparation of the given active compound until dripping wet.

mites (Tetranychus telarius in all stages of development.

TABLE 4 [Plant-damaging insects] Concentration Degree of of active destruction compound in in percent Active compound percent after 8 days (241) Cl 0. 2 100 C N 0. 02 100 N-N=C l C O :-C H;

(251) Cl 0. 2 100 /C N 0. 02 100 NN=C l All H C Or-CQH5 (260 ON 0.2 100 g 0. 02 100 F|C H N-N=C 0 ill 0 0 3-0 H;

EXAMPLE Tetranychus test Solvent: 3 parts by weight dimethyl formamide.

Emulsifierz 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of the particular active compound, 1 part by Weight of such active compound 40 is mixed with the stated amount of solvent containing the stated amount of emulsifier and the resulting concentrate is diluted with water to the desired final concentration.

After the specified period of time, the cflectiveness of the preparation of the given active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: 100% means that all the spider mites are killed whereas 0% means that none of the spider mites are killed.

The particular active compounds tested, their concentrations, the evaluation time and the results obtained can be seen from the following Table 5:

TABLE 5 [Plant-damaging mites] Concentration Degree of of active destruction compound in in percent Active compound percent after 8 days (A) c1 0. '2 /CN 0. 02 0 N-N=C & CN

(known) (271) CN 0. 2 0. 02 60 r H 0-0 G H: FaC ii 0 (28 C N 0.2 98 0. 02 80 F a C IIIN= C H (Ir-OCH:

(1;) F30 0. 2 100 C N 0. 02 100 0. 002 so -II\ N=C n (ll-OCH:

'with several liters of water.

17 EXAMPLE 6 A further test was carried out in the same manner as Example and the results are set out below in Table 6:

ing up with methylene chloride. After drying and distilling off of the methylene chloride, 122 g. (76% of the theory) of a-cyano-a-carboethoxy carbonyl-2,4,S-trichloro-phen- TABLE 6 [Plant-damaging mites] Concentration Degree 0t of active destruction compound in in percent Active compound percent after 8 days Cl 0. 2 100 (35') CN 0.02 as C1 N-N=C C-C H: 1 ll C1 N-N=C\ 1k C-CHI Ft 1| FrC-S N-N=C\ l cor-on,

EXAMPLE 7 ylhydrazone are obtained. Recrystallization from ethanol F's gives yellow needles of MP. 133134 C.

EXAMPLE 9 N-N=C G1 I A, H E 13c NHN=C com 115 g. 3,5-di-(trifluoromethyl)-aniline are diazotized in 400 ml. of 85% H PO with 157.5 g. of 41% nitrosylsulfuric acid at 5-l0 C. After diazotization, the mixture is diluted with 1000 ml. of water and filtered. This diazonium salt solution is added dropwise at 010 C., with stirring, to a mixture of 49.5 g. cyanoacetic acid methyl ester in 1000 ml. of acetic acid and 1.1 kg. sodium acetate. In the mixture a pH value of 5 is maintained by further addition of aqueous sodium acetate solution. After completion of the addition of the diazonium salt solution, stirring is continued for 1 hour, and the precipitated product is filtered off with suction and washed The residue is taken up in methylene chloride, dried over sodium sulfate, and the residue obtained after the methylene chloride has been distilled off is recrystallized from white spirit. 136 g. (80% of the theory) of a-cyano-a-carbomethoxy-carbonyl-,35bis(trifluoromethyl)-phenylhydrazone are obtained as pale-yellow needles of M.P. 155 C.

EXAMPLE 8 98.5 g. 2,4,5-trichloroaniline are diazotized in 400 ml. of concentrated H 80 (d.=1.84) with 157.5 parts of 41% nitrosyl-sulfuric acid at 5-10 C. After diazotization, the mixture is diluted with 1000 ml. of chopped ice and filtered. This diazonium salt solution is then added dropwise at O15 C., with stirring, to a mixture of 57 g. cyanoacetic acid ethyl ester, 250 ml. acetic acid, 1500 ml. of ice water and 2 kg. sodium acetate. A pH value of 4-5 in the mixture is maintained by further addition of sodium acetate. Dilution with 1000 ml. of water is then etfected and stirring is continued for 1 hour. The precipitated product is filtered off with suction and the reaction product is separated from inorganic salts by tak- 195.5 g. (1 mol) 2-chloro-5-(trifluoromethyl)-aniline are dissolved in 5 60 g. of concentrated hydrochloric acid. Part of the hydrochloride precipitates. The suspension is added to 1.8 kg. of ice and 1200 ml. of water and diazotization is efiected rapidly at 0 C. with 72 g. (1.05 mols) sodium nitrite in 160 ml. of water. The solution of the diazonium salt is filtered and added dropwise at 0-5" C. to a mixture of 134.5 g. (1 mol) of a-chloro-acetylacetone in 600 ml. ethanol and 500 g. potassium acetate in 800 ml. of water. During coupling, the pH value was kept to about 6 by the addition of further potassium acetate. The ice cooling is removed and stirring is continued for 4 hours; suction filtration is effected followed by washing thoroughly with water and recrystallization from ethanol. 183 g. (61%) a. chloro-a-acetyl-carbonyl-Z-chloro-S- (trifluoromethyl)-phenylhydrazone are obtained as pale yellow crystals of M.P. 151-153" C.

To 400 ml. of phosphoric acid there are added slowly, at 10 C., 157.5 g. nitrosyl-sulfuric acid (42%, d.=1.905). 98.2 g. (0.5 mol) 2,4,5-trichloro-aniline are introduced into the mixture at 5-10 C. Stirring is effected for 3 hours at 10 C., followed by filtration. The diazonium salt solution is then added dropwise to a mix ture of 104.5 g. a-bromo-acetoacetic acid ethyl ester, 900 ml. ethanol, 2 kg. ice and 1.1 kg. sodium acetate. The pH value is kept to 5-6 by possible further addition of sodium acetate. After completion of the diazonium salt solution, stirring is continued at 10-20 C. for 4 hours, followed by dilution with 4000 ml. of water and suction filtration. The residue on the filter is washed well with water and recrystallized from ethanol. 23.5 g. (45%) a-bromo-a- EXAMPLE 11 CN NH-N=C/ 01 (3,) 29.9 g. (0.1 mol) a-acetyl-a-chloro-carbonyl-2-chloro- 5-(trifluoromethyl) phenylhydrazone (prepared as described in Example 9) are dissolved in 300 ml. dimethyl formamide and added dropwise at room temperature, with vigorous stirring, to a solution of 7.1 g. (0.11 mol) KCN and 5.6 g. (0.1 mol) KOH in 750 ml. of water. After completion of the dropwise addition, stirring is continued for minutes, and activated charcoal is added; filtration is etfected and the filtrate is acidified with glacial acetic acid. The precipitate is filtered off with suction, washed with water and dried. 41.0 g. (85%) u-cyano-aacetyl-carbonyl-Z-chloro 5 (trifluoromethyl)-phenylhydrazone are obtained in the form of a pale yellow powder which, for purification, can be recrystallized from ethanol. M.P. 114-l18 C.

TABLE 12-C0ntinued X Y Z M. C.

3,5-(CF3): 107-109 3,5-(CF1): -1 8 2,6-C14, 4-NQ: 106-111 2-01 1, 5-01 138-139 3,5(011): 3- 5 2-Cl 135-136 2-01 92-94 4-C1 160-172 3,4-01 224-225 3,4-Cl: 158-159 2-Cl, 5-CF1 114-115 2,4501, 5 3,5-(01'51): 184-181 3,5-(CF1): 122-124 2,6-(CH1): 72-74 2,6-(CH1), 42-43 3,5-(CF02, K-Salt l 235 2-01 118 4-C1 172-174 2-01, 5-01; 138-140 2,6-(CH3): 107-110 2,6-(CHz): 199 2-01, S-CFI 214 2-01, 5-01; 149-151 2,4501; 117-119 1 Decomposition.

EXAMPLE 13 In a manner analogous with that described in Examples EXAMPLE 12 7-12, the following compounds according to Formula I above can be prepared: TABLE 13 oca Y Z M.P., C: (391) on 201, 501. 114-118 CH: 4-01 223-231 34.5 g. (0.15 mol) a-acetyl-a-chloro-carbonyl-2-chloro- CH1 0H. 3-01 188-190 phenylhydrazone, prepared in a manner analogous to 121- CH, 3,4-011 202-203 ample 9, are dissolved in 500 m1. methanol, and 13.0 g. gg; g g-1g 331?, sodium azide (0.2 mol) are added. The mixture is boiled CH; 2 01, 0-0111 1 5-118 under reflux for 3 hours, with stirring; filtration from the 8g; precipitated sodium chloride is effected and the filtrate is CH. 2N0. 199-201 concentrated to about one-fifth'of the original volume. CHI 268469 CH; a-01,4-No, 222-223 After cooling, the precipitated crystals are filtered 0E 40 CH; 3-NO4,4-C1 247-248 with suction and washing is etfected with water, then with 8%: gggf; $9,; 176.178 cold methanol. 23.5 g. (66%) a-aZido-a-carbonyI-Z- 0H. 214-010,), 150-151 chloro-phenylhydrazone are obtained in the form of a 'Q 149-150 CH1 2,0- 0 1), 125-129 pale brown crystalline substance which, for further purt- 8%, 2, 482%? 26 :3?

2,6- 0 s ficat on, can be recrystallized from ethanol. M.P. 121 3 W247 122 C., decomp. (9 833E) gsomm eom 122-12g a -01 In a manner analogous with that described in Exam 0(0111); 3,5-01, 2 ples 7-12, the fOllOWlng compounds according to For- Cgffiig; g ggi f g-2E l1 mula I above can be prepared. (100) -2g I I,

TABLE 12 0(0110; 3,5(01 01 4- 0(0119. 2,4,5-0h 158-161 x Y z M.P., 0. 0H. 4-SCF; 155-159 CH: 2-SCF: 2-01, 5-CF: 120-124 CH: 2-so40F 174-175 201,502; 143 C(CHQ! 4- 1 88-9 2,4501; 197 001E, 260201111, 5-019: 167-168 354010): 154 00,11, 200m, 4-Nol, 5-011. 205 2,001,, 4-N0! 140-147 00,11, 20011,, 4-01, 50H; 149-152 2,501,, 4-N0, 159-100 0041!; 20m, 4-01 98-100 ,5011. 4-N01 157 00,121 3,501: 131-135 2,5014, 4-N0, 168 00H, 2,a,4,5 0-011 141 2,4-No, 183-184 OCH 2-so=0,Ht, 5-013 187-189 400,011; 139 OCH 20cm, 4-NO4, 5-0111 1 2-011, 0N0, 142-140 00H. 20011., +01, 5-011; 150-152 2,5-C12,4-SOz-N(CHJ): 100-153 60 (as. 0011. 55-01, 195-197 2-Cl, 4-CF: 1&6 OCH 4-SCFI 123 25-011, 4-CF: -117 OCH; 2-5-01? 99-100 2,501,, 4-CF: 122 OCH: 4-SO1CF: 145-150 2,3,4501. 139 OCH: 3-CHF;, 4-01 2-F, 5-01; 99-101 CH1 4-S-CC1F: 90 2-011; 117-118 2-CF: 156-157 5 {fig It will be realized that all of the foregoing compounds 4-0F -136 contemplated by the present invention possess the desired 4-013 115 151 selectlve pesticidal, especially arthropodlcldal, i.e. insecti- 149 cidal or acaricidal, properties for combating insects and 2-CF, 4-01 173-174 141 70 acarids, and that such compounds have not only a very g'ggm g3 slight toxicity toward warm-blooded creatures, but also a 222 concomitantly low phytotoxicity. 3,4-(CN) 2 CN H110, "(H79 As may be used herein, ie both in the specification 3,5491%), 2 and dams, the terms arthropod, anthropodicidal and 6 133434 75 arthropodicide" contemplate specifically both insect and acarids. Thus, the insects and acarids may be considered herein collectively as arthropods to be combated in accordance with the invention, and accordingly the insecticidal and/or acaricidal activity may be termed anthropodicidal activity, and the concomitant combative or effective amount used will be an arthropodicidally effective amount which in effect means an insecticidally or acaricidally effective amount of the active compound for the desired purposes.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention which is to be limited only by the scope of the appended claims.

What is claimed is:

1. A method of combating arthropods which comprises applying to such arthropods or their habitat an arthropedically etfective amount of a compound of the formula in which X is selected from the group consisting of halo, cyano and nitro,

Y is selected from the group consisting of alkyl having 1-4 carbon atoms, alkoxy having 14 carbon atoms and --NRR' in which R and R each individually is selected from the group consisting of hydrogen and alkyl having l-3 carbon atoms,

Z is selected from the group consisting of alkyl having 1-4 carbon atoms, halo, nitro, cyano, trifluoromethyl, trifluoromethylmercapto, trifiuoromethylsulfonyl, trifluoromethylsulfoxyl, alkylsulfonyl having l-4 carbon atoms, dimethylamino sulfonyl and alkoxy having 1-4 carbon atoms, and

m is a whole number from l-S, or

the alkali metal, alkaline earth metal or the amine salt thereof,

alone or in admixture with a solid or liquid diluent or carrier.

2. The method of claim 1 in which Y is selected from the group consisting of alkyl and alkoxy having 1-4 carbon atoms,

each individual Z is selected from the group consisting of methyl, trifluoromethyl, trifluoromethylmercapto, chloro, nitro and cyano, and

m is a whole number from 1-3.

3. The method of claim 1 wherein such compound is a-cyano a carbomethoxy-carbonyl 3,5 bis(trifiuoromethyD-phenylhydrazone having the formula 4. The method of claim 1 wherein such compound is a cyano-a-acetyl-carbonyLZ-chloro-5-(trifluoromethy1)-phenylhydrazone having the formula COCH:

H C-OCIE 6. The method of claim 1 wherein such compound is a cyano-a-acetyl-carbonyl-4-(trilfluoromethylmercapto)- phenylhydrazone having the formula 7. The method of claim 1 wherein such compound is a-chloro in acetyl-carbonyl-2,6-dimethyl-phenylhydrazone having the formula CHO QE K 8. The method of claim 1 herein such compound is a-cyano-a-carbomethoxy carbonyl 4 (trifluoromethylsulfonyl)-phenylhydrazone having the formula mo- 1% Gimme:

9. An arthropodicidal composition comprising arthropodically effective amounts of a compound having the formula Cos-CHI in which X is selected from the group consisting of halo, cyano and nitro,

Y is selected from the group consisting of alkyl having 1-4 carbon atoms, alkoxy having 14 carbon atoms and --NRR' in which R and R each individually is selected from the group consisting of hydrogen and alkyl having 1-3 carbon atoms,

Z is selected from the group consisting of alkyl having 1-4 carbon atoms, halo, nitro, cyano, trifiuoromethyl, trifluoromethylmercapto, trifiuoromethylsulfonyl, trifluoromethylsulfoxyl, alkylsulfonyl having 1-4 carbon atoms, dimethylamino sulfonyl and alkoxy hav-- ing 14 carbon atoms, and

m is a whole number from l-S, or

the alkali metal, alkaline earth metal or the amine salt thereof,

in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier and a surface-active agent.

10. The composition of claim 9 wherein such compound is selected from the group consisting of: 

